Azo dyestuffs



Patented July 2, 1935 UNITED STATES:

PATENT OFFICE AZO DYESTUFFS V Hans Krzikalla, Ludwigshaien-on-the-Rhine, and

Bernhard Eistert, Mannheim,

Schmitt, Darmstadt,

and Robert and Herbert Kracker,

Frankfort-on-the-Main-Hochst, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation oi Delaware No Drawing. Application December 6, 1933, Serial No. 701,232. In Germany December 13 Claims. (Cl. 260-76) The present invent-ion relates to new waterinsoluble azo dyestuffs and a process of producing same. I

We have found that valuable water-insoluble azo dyestuffs are obtained by coupling with a diazo compound which is free from groups causing solubility in water ('i. e. free from sulphonic' and carboxylic acid groups) an ortho-hydroxy carboxylic acid arylide corresponding to the general formula T wherein Y stands for an aryl radicle, Z for a substituent containing a group capable of enolization and wherein to the benzene nucleus marked A a nuclear system containing at least one para (2 ,3-hydroXynaphthoy1amino)-benzoylacetic acid anilide para (2,3-hydroxynaphthoylamino)-benzoylacetoue 1-(2',3-hydroxynaphthoylamino)-4- (acetoacetyl-amino)- benzene nucleus is attached in the positions marked X. The group Z may be for example COCH2COCH3, NHCO'CHzCO'CH3,

CO-CH2-CO-NI-I-R V (wherein R rep-resents an aryl radicle) and pyrazolone radicles such as the radicle of methylpyrazolone. I

Q "Q Q invention are those derived from 2,3-hydroxy naphthoic acid, for example oo-om-o 0-NH-Q,

CONH

ooNn III =0 "The corresponding compounds containing an anthracene radicle instead of the naphthalene radicle shown are very suitable also. i

The ortho-hydroxy carboxylic acid ary'lide's or the kind defined above when applied in alkaline solutions possess 'a substantially better allinity to the .fibre than 'ortho-hydroxy carboxylic. acid arylides free from groups capable of en'olization and are much more fertile than the latter. In

t Q-GHz.

' fined above may be prepared by causing the corresponding ortho-hydroxy carboxylic, acids, their anhydrides, esters or halides to react with primary or secondary aromatic amines containing a group capable of enolization. V The reaction may be effected in the presence of solvents such as toluene or pyridine.

ner usual in the production of development dyestuffs, the fibre being first soaked with a solution of the coupling component and subsequently handled in a bath containing an excess of the diazo compound. It is preferable to effect the coupling in alkaline solutions. The dyestuffs may also be prepared in the absence of fibres whereby valuable pigments are formed.

The following examples will further illustrate the natureof this invention but the invention is not restricted to these examples.

Example 1 bic centimeters of an aqueous solution of sodium hydroxide of 28 B strength and 10 cubic centimeters of Turkey red oil. The yarn bottomed is introduced, if desired after rinsing for a short time, into a bath containing 3 per cent of the diazonium chloride of 4-amino-4-methoxy-diphenylamine. After soaping and rinsing a deep black dyeing of good fastness properties is ob tained-.-

-If the yarn bottomed as described in the preceding paragraph is handled ina bath containing 4 per cent of the diazonium chloride of 3-amino-4-methoxy-6-benzoylamino-l-methylbenzene or 2.5 per cent of the diazonium chloride of l-amino-4-nitrobenzene, dyeings of bean tiful fast red-brown shades or of strong red shades respectively are obtained. If cotton yarn is treated as described in the first paragraph of the present example while r'eplacingthe coupling component described there in by the corresponding compoundsderived from 2.3-hydroxy carbazole carboxylic acid or 2,3-hydroxyanthracene carboxylic acid instead of 2,3-

hydroxynaphthoic acid, similar black dyeings are obtained. V l

' W Example 2 l'mol'ecular proportion of 1-[4-(2",3"-hydroxynaphthoylamino) phenyl] 3 methyl-5- The dyestuffs may be.

prepared in the presence of the fibre in the manacetic-acid-2.4-dimethoxy 5 chloranilide with .2,3-hydroxynaphthoic acid chloride). opment by means of a solution containing 5 per cent of the diazonium chloride of 4-amino-3- 7 Example 3 ONH OCH| OOMWNHQ (obtainable by condensing meta-aminobenzoyl- By develmethoxy-diphenylamine, a dyeing of strong yellow-brown shade I is obtained which possesses very good fastness to washing and boiling with sodium carbonate solution. If development is effected with a solution containing 4 per cent of the diazonium chloride of 3-amino-4-methoxy-6-benzoylamino-l-methylbenzene red-brown shades of similar fastness properties are obtained.

Example 4 CONE-O-NH-CO-CHz-CO-CH:

(obtainable by condensing aceto-acetic-acidpara-aminoanilide with. 2,3-hydroxynaphthoic acid chloride). lution containing 3 per cent of diazotized lamino-2-methoxy-benzene-5-su1phonic acid-diethylamide strong-fast red shades are produced.

Example 5 I Cotton yarn is bottomed as described in Example 1 by means of a solution containing per liter 1 gram of l-(2;3Ghydroxy-naphthoylamino) -3-acetoacetylamino-benzene obtainable by condensing aceto-acetic-acid-meta-aminoanilide with 2,3-hydroxynaphthoic acid chloride and corresponding to the formula Development is then eflected by means of a 4 per cent solution of the diazonium chloride of 1- amino-2.5-dichlorbenzene. orange shade of good fastness is obtained.

What we claim is:-

1. The process of producing water-insoluble azo dyestuffs which comprises coupling with an aromatic diazo compound an ortho-hydroxy' car A dyeing of brilliant By development with a diazo soboxylic acid arylide corresponding to the general formula wherein Y stands for an aryl radicle of the benzene series, Z for a substituent containing a -CH2-CO- group capable of coupling and wherein to the benzene nucleus marked A a nuclear system containing at least one nucleus is attached in the positions marked X.

2. The process of producing water-insoluble azo dyestuffs which comprises coupling in an alkaline medium with an aromatic diazo compound an ortho-hydroxy carboxylic acid arylide corresponding to the general formula wherein Y stands for an aryl radicle of the benzene series, Z for a substituent containing a CH2CO- group capable of coupling and wherein Y stands for an aryl radicle of the henzene series, Z for a substituent containing a -CH2CO group capable of coupling, wherein R stands for an aromatic radicle and wherein the azo group attached to Z is connected with the methylene group.

6. The water-insoluble azo dyestuif corresponding to the formula wherein to the benzene nucleus marked A a nuclear system containing at least one nucleus is attached in the positions marked X.

3. The process of producing water-insoluble azo dycstufis which comprises coupling with an aromatic diazo compound a 2,3-hydroxynaphthoic acid arylide with an aryl radicle of the benzene series to which radicle a substituent is attached which contains a CI-I2CO group capable of coupling.

CHaO

7. The water-insoluble azo dyestufi corresponding to the formula -OONH OHaO CHaO 8. The water-insoluble azo dyestuff corresponding to the formula 4. Water-insoluble azo dyestuifs corresponding to the general formula III=NR X /0H CHsO a 9. Fibres dyed with the dyestuffs according to claim 4.

10. Fibres dyed with the dyestuffs according to claim 5.

claim 6.

12. Fibres dyed claim '7.

13. Fibres dyed with the dyestufi according to claim 8. HANS KRZIKALLA. BERNHARD EISTERT. ROBERT SCHMI'I'I. HERBERT KRACKER.

with the dyestiifi according tq 

